CN114775096A - Method for producing regenerated nylon-6 fiber by adopting solid-phase polycondensation direct spinning technology - Google Patents
Method for producing regenerated nylon-6 fiber by adopting solid-phase polycondensation direct spinning technology Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyamides (AREA)
Abstract
The invention provides a preparation method for producing regenerated nylon-6 fiber by adopting a solid-phase polycondensation direct spinning technology. Respectively collecting blocky waste materials or waste silk generated in the production process of nylon 6 according to the glossiness of slices, crushing the blocky waste materials or waste silk by using a crusher or a fiber cutting machine, then putting crushed particles or short fibers into a pre-drying tower for drying, putting the dried particles into a polycondensation tower for solid-phase polycondensation, adding a small amount of catalyst, controlling the polycondensation temperature and the polycondensation time, directly feeding the materials into a screw extruder for melting after the polycondensation is finished, extruding the melted polymer fluid from a spinning assembly after being metered by a metering pump, solidifying and forming fibers after blowing cooling, and then winding and forming after oiling, networking and drafting. Compared with the traditional chip spinning regenerated nylon 6, the method can improve the product quality of the regenerated nylon 6, improve the production efficiency, avoid repeated hot processing of regenerated raw materials and reduce the energy consumption.
Description
Technical Field
The invention relates to the field of regenerated fibers, in particular to a production method of regenerated nylon-6 fibers.
Background
The cyclic regeneration of the chinlon is an important way for improving the utilization rate of resources and solving the shortage of fossil resources. The method for recycling the nylon refers to the steps of recycling waste polyamide finished products or semi-finished product raw materials, and re-processing the waste polyamide finished products or semi-finished product raw materials by physical or chemical means to prepare the polyamide fiber. The regenerated nylon can be divided into a pre-consumption raw material and a post-consumption raw material according to the recycling stage, and the classification is based on whether the recycled raw material is a semi-finished product before being used by a consumer or a finished product after being used by the consumer. The recovery and reduction degree can be divided into monomer recovery and polymer recovery, and the classification is based on whether the recovered raw material is reduced to monomer and then polymerized to obtain regenerated polymer or the recovered polymer is directly utilized to produce regenerated fibers. The raw materials for producing the post-consumer regenerated nylon comprise wastes such as fabrics, clothes, carpets and fishing nets made of nylon, for example, Chinese patent CN107056625 discloses a method for recovering hexamethylene diamine from polyamide 66 waste fishing nets, and Japanese patent JP2008031128A discloses a method for recovering caprolactam from nylon 6 fiber wastes. The advantages of post-consumer recycling are that the amount of raw materials available for recycling is large, the resource recycling level is high, the disadvantages are that sorting and classification of the raw materials after consumption are troublesome, and the raw materials are generally recycled to monomer level by a chemical method and then polymerized again, the recycling process is complex, the energy consumption is high, the final cost is high, and the large-scale application is limited.
Another relatively mature scheme for recycling regenerated nylon is to recycle the nylon before consumption, wherein the recycling before consumption is obtained by recycling waste materials generated in the nylon production process, reducing the waste materials into regenerated polyamide again by adopting methods such as melting processing and the like, and then carrying out melt spinning. According to estimation, due to the influence of factors such as starting, spinning modification, testing and the like, waste materials accounting for 2-5% of the total production amount can be generated in the production process of chinlon 6, and the waste materials have three sources: the first type is block waste which is generated by flushing a pipeline and is cooled into blocks after a polyamide melt is extruded through a screw die orifice; the second type is the releasing waste silk which is generated in the spinning preparation process and is formed by cooling the polyamide melt through spinning fine flow formed by a spinneret plate component; the third type is winding waste silk, which is waste silk generated in the winding preparation process and is generated in the processes of cooling, oiling, drafting and winding by spinning trickle. Compared with the post-consumption regenerated nylon, the pre-consumption regenerated nylon has the advantages that the recovery process is relatively simple, and the energy consumption is relatively low, although the recyclable resources are limited, namely only waste materials generated in the nylon production process can be recycled, and the resource recycling level in the whole industrial chain is relatively low, namely only semi-finished product resources at the front end of the textile industrial chain can be recycled. Chinese patents CN 201510200462.2 and CN 201710557878.9 respectively disclose a method for preparing polycaprolactam slices by recycling nylon waste yarns. U.S. Pat. No. 5, 4143001 also discloses a method for melting and granulating nylon waste yarn after recovery and cutting. Chinese patent CN 202110026882.9 discloses a method for producing regenerated nylon 6 by dissolving nylon 6 waste with a mixed solvent, filtering and purifying to obtain nylon 6 crystals, and then carrying out melt spinning to produce regenerated nylon 6. In general, only the raw materials are reduced into polymers in the recovery before consumption, and only a few technical schemes select to reduce the raw materials recovered before consumption into monomers and then repolymerize the monomers to obtain the polyamide. Chinese patent CN 201310434072.2 discloses a method for depolymerizing waste nylon yarn at high temperature and recovering caprolactam by using phosphoric acid as a catalyst and potassium permanganate and sodium hydroxide as auxiliaries.
At the present stage, two main reasons for limiting the development of the regenerated nylon-6 before consumption are provided, one is the quality problem and the other is the energy consumption problem. The quality problem is caused by the degradation of macromolecules of the polymer raw material in the melt processing process, the increase of the content of the oligomer can deteriorate the spinning condition, and the quality of the chinlon 6 can be influenced. The reason for the degradation of macromolecules is that the ring-opening polymerization of caprolactam to polycaprolactam is a reversible process, and the high temperature makes the equilibrium of the reaction proceed toward the formation of monomers, as shown in FIG. 1 and FIG. 2 (synthetic fiber production technology, Dong Ji et al, Press of textile industry, second edition 1993, page 196; Polyamide fiber, Zhu Jianmin, Press of chemical industry, first edition 2014, page 86). The energy consumption problem is that the nylon-6 waste is generated in the process of spinning and fiber forming from the recovery, and the energy consumption is increased by the increase of process steps and the multiple thermal processing of raw materials or working media. The method can be divided into two parts, wherein the first part comprises the energy consumption required by recovering the waste material until granulating to obtain the polycaprolactam regenerated raw material, the second part is the energy consumption required by melting the polycaprolactam regenerated raw material to spinning to obtain the chinlon 6, and the energy consumption generated by the second part is inevitable, but the energy consumption of the first part can be reduced by improving the process technology level. Generally, energy consumption can be controlled to be relatively low by directly drying recovered waste materials, then performing melt granulation and then chip spinning, but the method has the disadvantages that polycaprolactam raw materials are subjected to 3 times of melt thermal processing before being spun into nylon 6, firstly, primary chips are melted to obtain polycaprolactam blocky or fibrous waste materials, secondly, the waste materials are subjected to melt processing and are changed into polycaprolactam regenerated chips, thirdly, the polycaprolactam regenerated chips are melt spun to obtain regenerated nylon 6, polycaprolactam is degraded in each round of melt thermal processing, and finally, the production efficiency and the product quality of the regenerated nylon 6 are seriously influenced. The other technical route is to perform tackifying or viscosity regulation on the chinlon 6 waste after drying the waste, remove monomers and oligomers, and perform melting granulation, so that the molecular weight of the obtained regenerated polycaprolactam slices can reach the standard of primary slices, thereby ensuring the product quality of the regenerated chinlon 6. Chinese patent CN 202110033445.X discloses a method for obtaining nylon 66 slices by taking nylon 66 waste filaments as raw materials through two-stage melt mixing, drying, tackifying and then carrying out melt spinning to obtain nylon 66, and the method relates to a process route which comprises the steps of recycling the nylon 66 waste filaments, melting to prepare slices, drying, tackifying and then carrying out melt spinning again, and has a relatively long process and relatively high energy consumption.
The invention effectively solves the problems by combining the solid-phase polycondensation and the direct spinning technology from the two aspects of improving the quality and reducing the energy consumption. Solid phase polycondensation is a method of further polymerizing a polymer material below the melting point of the polymer under the action of a catalyst, and is one of effective ways of increasing the viscosity of the polymer (polyamide fiber, zhu jian, chemical industry press, first edition 2014, page 41). U.S. Pat. No. 3, 2993879 disclosed a solid phase polycondensation method of polycaprolactam as early as 1961, and British patent No. GB1305246A disclosed a method of increasing the viscosity of polycaprolactam by solid phase polycondensation using phosphoric acid as a catalyst. In these disclosed methods, Solid phase polycondensation is usually used to increase the molecular weight of polycaprolactam at the later stage of Polymerization, and the principle is to control the polycondensation temperature below the melting point of polycaprolactam and above the melting point of caprolactam monomer, and to make the caprolactam monomer undergo ring-opening Polymerization to form polycaprolactam polymer under the action of catalyst, and the appropriate temperature makes the polycondensation equilibrium proceed toward the direction of polycaprolactam polymer formation, and ensures that the polycaprolactam polymer formed will not be degraded (Solid State Polymerization, Constantine paspalyparides, John Wiley & Sons, inc., 2009, Page 123-124). The key of polycaprolactam solid phase polycondensation is the temperature, the catalyst and the particle size of the raw materials, and in a proper temperature range, only if the particle size of the raw materials is small enough, enough monomers and oligomers can be diffused from polycaprolactam macromolecules in softened polycaprolactam particles to participate in polycondensation. Solid phase polycondensation has not been used to recover polycaprolactam waste on a large scale, because it requires high recovery of raw materials, which generally only contain polycaprolactam macromolecules, caprolactam monomers or oligomers composed of caprolactam monomers, and a small amount of inert matting agent, while the polycaprolactam waste after consumption contains many impurities, such as dyes, dyeing and finishing aids, and other impurities, which are difficult to achieve.
An important factor hindering the popularization of the nylon-6 melt direct spinning technology is that the production of polycaprolactam slices and the production of nylon-6 are separated in most cases, and how to reduce the oligomer content of the polymer system in the molten state and the retention time of the polymer system in the molten state is a very difficult problem in the technical aspect. Chinese patent CN 105669969B discloses nylon 6 and a method for preparing nylon 6 by melt direct spinning thereof. Chinese patent CN 109811423B discloses a method for producing functional polyamide fiber by continuous polymeric melt direct spinning. According to literature reports that chinlon 66 realizes breakthrough of a melt direct spinning technology, after a preliminary test, the energy consumption is reduced by 3.4% (practice of energy saving and consumption reduction in the production process of melt direct spinning of polyamide 66, namely, lie peng xiang, synthetic fibers, 2021, 50(8), 11). So far, no patent technology for preparing regenerated nylon 6 by using a direct spinning technology is disclosed.
Therefore, for those skilled in the art, how to recover various waste materials generated in the nylon production process, and how to improve the quality of regenerated nylon-6 fiber, improve the production efficiency and reduce energy consumption becomes a problem of further research in the industry.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a production method of regenerated nylon-6 fiber, which can improve the product quality of the regenerated nylon-6 and improve the production efficiency through a new process design, and can avoid repeated hot processing of regenerated raw materials and reduce energy consumption.
In order to realize the aim, the technical scheme adopted by the invention is a production method of regenerated nylon-6 fiber, which comprises the following steps:
and (3) recovering raw materials: separately collecting waste materials generated in the production process of nylon 6 to obtain blocky waste materials and/or filiform waste materials;
pretreatment of the reclaimed materials: chopping the lumpy waste material and/or the filiform waste material;
pre-drying: feeding the pretreated massive waste and/or filamentous waste into a pre-drying tower from the top of the tower, and simultaneously introducing high-temperature nitrogen from the bottom of the pre-drying tower, wherein the nitrogen carries water vapor to flow out of the top of the tower and enter a recovery system;
solid phase polycondensation: the dried and softened massive waste and/or filamentous waste flows out of the bottom of a pre-drying tower, and then is fed into a solid phase polycondensation tower for polycondensation reaction, a catalyst is sprayed to the massive waste and/or filamentous waste from the top of the solid phase polycondensation tower, high-temperature nitrogen is introduced from the top of the solid phase polycondensation tower, the nitrogen flows out of the bottom of the solid phase polycondensation tower and enters a recovery system, and a regenerated nylon raw material in a softened state is obtained at a certain polycondensation temperature and polycondensation time; and
direct spinning: feeding the regenerated nylon raw material into a screw extruder directly for melting, extruding through a spinneret plate, oiling, drafting and winding to obtain the regenerated nylon-6 fiber.
The recovered raw materials come from waste materials generated in the production process of the chinlon and are separately collected according to the production flow and the fiber luster. They may be block wastes, produced by flushing pipes, from the polyamide melt after extrusion through a screw die, and cooled to blocks; they may also be filamentous waste materials, including in particular: the releasing waste silk is generated in the spinning preparation process and is formed by cooling the polyamide melt through spinning fine flow formed by a spinneret plate assembly; the winding waste silk is the waste silk generated in the winding preparation process and the waste silk generated in the cooling, oiling, drafting and winding processes of the spinning stream.
In one embodiment of the present invention, the pretreatment of the recycled material comprises pulverizing the lump waste to obtain particles having a particle size of 1mm or less.
In one embodiment of the present invention, the waste material is cut into 2-10 mm short fibers before the recovery material is pretreated.
In an embodiment of the present invention, the staple fibers need to be washed away with the degreasing agent before pre-drying.
In one embodiment of the present invention, in the pre-drying step, the temperature of the nitrogen gas in the pre-drying tower is 100-140 ℃ and the flow rate is 1000-5000 m3/h。
In one embodiment of the present invention, the water content of the pre-dried lump waste and/or filamentary waste is controlled to be 500 to 5000 ppm.
In one embodiment of the present invention, the polycondensation temperature is controlled to be 110-180 ℃ and the polycondensation time is controlled to be 3-10 h. Wherein the polycondensation temperature is further preferably 130 to 150 ℃, so that regenerated fibers with higher quality can be obtained.
In one embodiment of the present invention, the time taken for feeding the regenerated nylon raw material from the screw extruder to the extrusion spinneret during direct spinning is less than or equal to 10 min.
In one embodiment of the present invention, the temperature of the pre-drying tower is controlled to be 100-130 ℃, the temperature of the nitrogen gas in the pre-drying tower is controlled to be 100-140 ℃, and the temperature of the nitrogen gas in the polycondensation tower is controlled to be 120-180 ℃. The flow of nitrogen in the polycondensation tower is 100-1000 m3H, controlling the flow of nitrogen in the pre-drying tower to be 1000-5000 m3/h。
In one embodiment of the present invention, the content of the catalyst is 100 to 5000ppm of the total amount of the spinning melt.
In an embodiment of the present invention, the catalyst used in the solid phase polycondensation step is one or a mixture of any two or more of aqueous solutions of boric acid, phosphoric acid, potassium dihydrogen phosphate and potassium hydrogen sulfate.
The technical scheme has the following beneficial effects:
the method is suitable for recycling most of the waste materials generated in the nylon production process, including block waste materials for flushing pipelines, the releasing waste silk generated in the spinning preparation process and the winding waste silk generated in the winding preparation process, and can improve the resource utilization rate and reduce the dependence of human beings on petroleum resources.
Compared with the conventional regenerated nylon, the method of the invention applies the solid phase polycondensation technology to the recycling of nylon waste, can improve the molecular weight of the regenerated polycaprolactam raw material and ensure the quality of nylon 6 fiber, and the catalyst adopted by the invention has small addition amount and no adverse effect on the environment.
Compared with the conventional regenerated nylon, the method applies the direct spinning technology to the melt spinning of the regenerated nylon raw material, can reduce the time of high temperature of a spinning melt to the maximum extent, directly sends polycaprolactam macromolecules after solid-phase polycondensation into a screw extruder for melt spinning, does not need to carry out melt granulation and then carries out slice melt spinning, can effectively prevent the polyamide macromolecules after solid-phase polycondensation from degrading, and greatly reduces the energy consumption.
Drawings
FIG. 1 is a graph of the effect of polymerization temperature and polymerization time on polycaprolactam viscosity, cited in "fiber-forming vitamin production technology", page 196;
FIG. 2 is a graph showing the effect of the melt residence time on the extractables content in polyamide 6, cited on page 86 of Polyamide fibers;
FIG. 3 is a schematic process flow diagram of an embodiment of the present invention.
Detailed Description
The invention will now be further described with reference to the following examples and figures 1 to 3.
When the waste nylon-6 is recycled, the waste nylon-6 is recovered and used as a raw material for regenerating the nylon-6 fiber, so that an operator can prepare the waste nylon-6 before the solid-phase polycondensation according to needs. Generally comprises the following two parts:
(1) collecting the recovered nylon raw material: the waste materials generated in the production process of the nylon-6 can be mainly divided into three types: the first kind is block waste produced by flushing pipeline and formed by cooling nylon melt after being extruded by screw; the second type is releasing waste silk which is generated in the spinning preparation process and is formed by cooling a spinning trickle formed by a nylon melt through a spinneret plate component; the third type is winding waste silk, which is waste silk produced in the winding preparation process and produced in the cooling, oiling, drafting and winding processes by spinning fine flow. And (4) separately collecting the three types of waste materials according to the gloss of the nylon chip raw material.
(2) And (3) crushing the recycled nylon raw material: and respectively crushing the three spinning wastes according to the luster of the slices. For the massive waste, a roller crusher is directly adopted for multi-stage crushing, so that the final particles can pass through a vibrating screen with the aperture of 1 mm; for the discharged waste silk, directly cutting the discharged waste silk into short fibers of 0.2-1.0 cm by using a fiber cutting machine; and cutting the wound waste silk into short fibers of 0.2-1.0 cm by using a fiber cutting machine, and then washing with water at 40-60 ℃ to remove the oil agent.
Comparative example 1
In the comparative example, the production is of conventional Chinlon 6 with specification 40d/34 f.
The specification of a primary conventional semi-gloss slice is 2.5, the content of a methanol extractable matter is 0.3 percent, the water content is 720ppm, the slice is fed into a stock bin, the slice enters a screw extruder through the stock bin, the length-diameter ratio of a screw is 25, the slice is divided into 6 sections, the temperature of each section is controlled to be 252 ℃, 262 ℃, 265 ℃, 258 ℃ and 258 ℃ respectively, the slice is melted into a spinning melt, the spinning melt is extruded from a spinneret plate after being extruded into a metering pump through a pipeline for distribution and metering (the first round of melting thermal processing, the time that the melt stays in a melting state is 12 min), the crosswind temperature is 16.5 ℃, the wind speed is 0.45 m/s, the spinning melt is cooled into fibers, and then oiling, pre-networking, drafting, main networking and winding are carried out to obtain nylon 6 fibers, the full-roll rate is 98.5%, the titer is 40.2 den, the breaking strength is 5.6 g/d, and the breaking elongation is 44%.
Comparative example 2
In the comparative example, the regenerated nylon-6 is produced by a conventional slicing method, and the specification is 40d/34 f.
Cutting the recycled semi-gloss waste silk (subjected to one-round melting thermal processing, the time of the melt staying in the molten state is 12 min) into short fibers with the length of about 1cm, feeding a screw to melt, controlling the length-diameter ratio of the screw to be 24, dividing into 5 sections totally, controlling the temperature of each section to be 242 ℃, 252 ℃, 260 ℃, 262 ℃ and 262 ℃, selecting a proper die head to extrude the melt (the time of the melt staying in the molten state is about 5 min) through the second-round melting thermal processing, cooling the melt into strips through a water tank, cutting the strips into slices, drying the slices through hot air, blowing the slices into a storage tank for storage, and obtaining the regenerated slices with the relative viscosity of 2.2, the content of the extractables of 1.6 percent and the water content of 1000 ppm. Feeding the regenerated chips into a storage bin, feeding the chips into a screw extruder through the storage bin, wherein the length-diameter ratio of a screw is 25, the chips are divided into 6 sections in total, the temperature of each section is controlled to be 252 ℃, 262 ℃, 265 ℃, 258 ℃, 258 ℃ and 258 ℃, the chips are melted into a spinning melt, the spinning melt is extruded from a spinneret after being extruded into a metering pump through a pipeline for distribution and metering (the melt is subjected to melt thermal processing in a third wheel, the time for the melt to stay in a molten state is 12 min), the crosswind temperature is 16.5 ℃, the wind speed is 0.45 m/s, the spinning melt is cooled into fibers, and then the fibers are subjected to oiling, pre-networking, drafting, main networking and winding to obtain the nylon 6 fibers, wherein the full-up rate is 95.2%, the fineness is 40.2 den, the breaking strength is 5.2 g/d, and the breaking elongation is 38%.
Example 1
The comparative example adopts the solid phase polycondensation direct spinning technology to recover the blocky waste to produce the regenerated nylon 6 with the specification of 40d/34 f.
Collecting semi-bright blocky polyamide 6 waste, conveying to a pulverizer to pulverize step by step to about 1mm of particle size, conveying the particles to a vibrating screen, controlling the aperture of the vibrating screen to be 1mm, putting the particles passing through the vibrating screen into a pre-drying tower to dry, controlling the temperature of the pre-drying tower to be 105 ℃, accessing the temperature from the bottom of the tower to be 105 ℃, and controlling the flow to be 1800 m3H, hot nitrogen which carries water flows out of the tower top to enter a recovery system. Sampling from a discharge port at the bottom of the tower for moisture detection, sealing and storing to room temperature, and detecting the moisture content of 822 ppm. The dried nylon raw material flows out from the bottom of a pre-drying tower, is fed into a solid phase polycondensation tower from the top of the pre-drying tower, and is intermittently sprayed with a catalyst potassium dihydrogen phosphate aqueous solution from the top of the solid phase polycondensation tower, wherein the total dosage of the catalyst is controlled to be 300 ppm, nitrogen with the temperature of 130 ℃ and the flow rate of 200 m3/h is introduced from the top of the solid phase polycondensation tower, hot nitrogen flows out from the bottom of the tower and enters a recovery system, the temperature of the solid phase polycondensation tower is controlled to be 130 ℃, and the polycondensation time is 5 hours. A sample was taken from a drain hole at the bottom of the column for detection, and the sampled particles were in a softened state, and after standing at room temperature, the extractable content of methanol was 0.7%, the relative viscosity was 2.5, and the water content was 780 ppm.
The solid phase polycondensation particle raw materials are directly fed into a screw extruder, the length-diameter ratio of the screw is 25, the solid phase polycondensation particle raw materials are divided into 6 sections, the temperature of each section is controlled to be 252 ℃, 262 ℃, 265 ℃, 258 ℃, 258 ℃ and 258 ℃, the slices are melted into spinning melt, the spinning melt is extruded from a spinneret plate after being extruded into a metering pump through a pipeline for distribution and metering (the melt stays for 10min in a melting state), the crosswind temperature is 16.5 ℃, the wind speed is 0.45 m/s, the spinning melt is cooled into fibers, and then the fibers are oiled, pre-networked, drawn, main networked and wound to obtain the nylon 6 fibers, the full-wind rate is 98.8%, the fineness of the nylon 6 fibers is 40.1 den, the breaking strength is 5.4 g/d, and the breaking elongation is 45%.
Example 2
The comparative example adopts the solid phase polycondensation direct spinning technology to recover filiform waste to produce regenerated nylon 6 with the specification of 40d/34 f.
Collecting semi-bright waste silk, cutting into 0.5 cm short fiber with fiber cutter, drying in a pre-drying tower at 110 deg.C, introducing at 110 deg.C from the bottom of the tower, and allowing flow rate of 2000 m3H, nitrogen, hot nitrogen carrying water flows out of the tower top to enter a recovery system. Sampling from a discharge port at the bottom of the tower for moisture detection, sealing and storing to room temperature, and detecting the moisture content to be 960 ppm. The dried nylon raw material flows out from the bottom of the pre-drying tower, and is fed into a solid phase polycondensation tower from the top, a catalyst potassium dihydrogen phosphate aqueous solution is intermittently sprayed to the nylon raw material from the top of the solid phase polycondensation tower, the total dosage of the catalyst is controlled to be 400 ppm, the temperature is 135 ℃ from the top, and the flow is 250 m3The nitrogen gas/h and the hot nitrogen gas flow out from the bottom of the tower and enter a recovery system, the temperature of the solid phase polycondensation tower is controlled at 137 ℃, and the polycondensation time is 8 hours. Sampling from a discharge port at the bottom of the tower is used for detection, sampled particles are in a softened state, and the extractable content of the sampled particles is detected to be 0.8 percent after the sampled particles are placed to room temperature, the relative viscosity of the sampled particles is 2.6, and the water content of the sampled particles is 680 ppm.
The particle raw materials after solid phase polycondensation are directly fed into a screw extruder, the length-diameter ratio of the screw is 25, the length-diameter ratio of the screw is divided into 6 sections, the temperature of each section is controlled to be 252 ℃, 262 ℃, 265 ℃, 258 ℃, 258 ℃ and 258 ℃, the slices are melted into a spinning melt, the spinning melt is extruded from a spinneret plate after being extruded into a metering pump through a pipeline for distribution and metering (the time for the melt to stay in the melting state is 10 min), the crosswind temperature is 16.5 ℃, the wind speed is 0.45 m/s, the spinning melt is cooled into fibers, and then the fibers are oiled, pre-networked, drawn, main networked and wound to obtain the nylon 6 fibers, wherein the full-wind rate is 97.8 percent, the fineness is 40.0 den, the breaking strength is 5.5 g/d, and the breaking elongation is 42 percent.
Example 3
The comparative example adopts the solid phase polycondensation direct spinning technology to recover the blocky waste to produce the regenerated nylon 6 with the specification of 40d/34 f.
Collecting semi-light block polyamide 6 waste material, and conveyingGradually pulverizing to particle size of about 1mm, transferring to a vibrating screen, controlling the aperture of the vibrating screen to be 1mm, drying the granules passing through the vibrating screen in a pre-drying tower at 110 deg.C, introducing at 110 deg.C from the bottom of the tower, and controlling the flow rate to be 1600 m3H, nitrogen, hot nitrogen carrying water flows out of the tower top to enter a recovery system. Sampling from a discharge port at the bottom of the tower for moisture detection, sealing and storing to room temperature, and detecting the moisture content to be 810 ppm. The dried nylon raw material flows out from the bottom of a predrying tower, is fed into a solid phase polycondensation tower from the top of the tower immediately, and is intermittently sprayed with a catalyst phosphoric acid aqueous solution from the top of the solid phase polycondensation tower to the nylon raw material, wherein the total dosage of the catalyst is controlled to be 350 ppm, the temperature is 140 ℃ when the catalyst is connected from the top of the tower, and the flow is 400 m3The nitrogen gas/h and the hot nitrogen gas flow out from the bottom of the tower and enter a recovery system, the temperature of the solid phase polycondensation tower is controlled at 142 ℃, and the polycondensation time is controlled for 3 hours. Sampling from a discharge port at the bottom of the tower is used for detection, sampling particles are in a softened state, and after the sampling particles are placed to room temperature, the extractable content of methanol is detected to be 0.5%, the relative viscosity is 2.5, and the water content is 650 ppm.
The particle raw materials after solid phase polycondensation are directly fed into a screw extruder, the length-diameter ratio of the screw is 25, the length-diameter ratio of the screw is divided into 6 sections, the temperature of each section is controlled to be 252 ℃, 262 ℃, 265 ℃, 258 ℃, 258 ℃ and 258 ℃, the slices are melted into spinning melt, the spinning melt is extruded from a spinneret plate after being extruded into a metering pump through a pipeline for distribution and metering (the melt stays for 10min in a melting state), the crosswind temperature is 16.5 ℃, the wind speed is 0.45 m/s, the spinning melt is cooled into fibers, and then the fibers are oiled, pre-networked, drawn, main networked and wound to obtain the nylon 6 fibers, the full-wind rate is 97.5%, the fineness is 40.0 den, the breaking strength is 5.2 g/d, and the breaking elongation is 40%.
Example 4
The comparative example adopts the solid phase polycondensation direct spinning technology to recover the filiform waste material to produce the regenerated nylon 6 with the specification of 40d/34 f.
Collecting semi-bright waste silk, cutting into 0.5 cm short fiber with fiber cutter, drying in a pre-drying tower at 100 deg.C, 100 deg.C from the bottom of the tower, and 2000 m flow rate3H, hot nitrogen which carries water flows out of the tower top to enter a recovery system. Sampling from a discharge port at the bottom of the tower for moisture detection, sealing and storing to room temperature, and detecting the moisture content to be 1240 ppm. The dried nylon raw material flows out of the bottom of a predrying tower, is fed into a solid-phase polycondensation tower from the top of the predrying tower, and is intermittently sprayed with a catalyst potassium dihydrogen phosphate aqueous solution from the top of the solid-phase polycondensation tower, wherein the total amount of the catalyst is controlled to be 400 ppm, nitrogen with the temperature of 142 ℃ and the flow rate of 400 m3/h is introduced from the top of the solid-phase polycondensation tower, hot nitrogen flows out of the bottom of the tower and enters a recovery system, the temperature of the solid-phase polycondensation tower is controlled to be 150 ℃, and the polycondensation time is 10 hours. Sampling is carried out from a discharge port at the bottom of the tower for detection, sampled particles are in a softened state, and the extractable content of the sampled particles is detected to be 0.5 percent after the sampled particles are placed to room temperature, the relative viscosity of the sampled particles is 2.6, and the water content of the sampled particles is 860 ppm.
The solid phase polycondensation particle raw materials are directly fed into a screw extruder, the length-diameter ratio of the screw is 25, the solid phase polycondensation particle raw materials are divided into 6 sections, the temperature of each section is controlled to be 252 ℃, 262 ℃, 265 ℃, 258 ℃, 258 ℃ and 258 ℃, the slices are melted into spinning melt, the spinning melt is extruded from a spinneret plate after being extruded into a metering pump through a pipeline for distribution and metering (the melt stays for 10min in a melting state), the crosswind temperature is 16.5 ℃, the wind speed is 0.45 m/s, the spinning melt is cooled into fibers, and then the fibers are oiled, pre-networked, drawn, main networked and wound to obtain the nylon 6 fibers, the full-wind rate is 98.3%, the fineness is 40.1 den, the breaking strength is 5.4 g/d, and the breaking elongation is 44%.
The key parameters of comparative examples 1-2 and examples 1-4 are shown in Table 1.
TABLE 1 comparison of key parameters for comparative examples and comparative examples
| Parameter(s) | Comparative example 1 | Comparative example 2 | Example 1 | | Example 3 | Example 4 |
| Starting materials | Primary section | Regenerated section | Lump waste | Filiform waste | Lump waste | Filiform waste |
| Spinning method | Spinning of chips | Spinning of chips | Direct spinning technology | Direct spinning technology | Direct spinning technology | Direct spinning technology |
| Water content ppm before spinning | 720ppm | 1000ppm | 780ppm | 680ppm | 650ppm | 860ppm |
| Viscosity before spinning dL/g | 2.5 | 2.2 | 2.5 | 2.6 | 2.5 | 2.6 |
| EX% before spinning | 0.3 | 1.6 | 0.7 | 0.8 | 0.5 | 0.5 |
| Percentage of full lap% | 98.5 | 95.2 | 98.8 | 97.8 | 97.5 | 98.3 |
| Breaking Strength g/d | 5.6 | 5.2 | 5.4 | 5.5 | 5.2 | 5.4 |
| Elongation at break% | 44 | 38 | 45 | 42 | 40 | 44 |
The pre-spinning viscosity represents the molecular weight of the nylon macromolecule, and as can be seen from table 1, the conventional regenerated chip is reduced compared with the original chip, which results in the quality deterioration of the nylon 6 product, while the pre-spinning viscosity of the regenerated raw material after solid phase polycondensation can basically return to the level of the original chip. Before spinning EX is the content of extractables in the raw materials and represents the content of oligomers in the nylon raw materials, the lower the content of the oligomers, the better the quality of the raw materials, the higher the production efficiency, and the better the quality of the spun nylon 6. From table 1, it can be seen that the extractable content of the regenerated raw material subjected to solid phase polycondensation is lower than that of the conventional regenerated chip and is close to the level of the virgin chip, and it can be seen that the production efficiency in the embodiment examples 1 to 4 is higher than that of the conventional regenerated chip, in which the full-package rate is improved, and the product quality, such as breaking strength and breaking elongation, of the regenerated nylon 6 is close to that of the nylon 6 spun from the virgin chip.
The invention effectively solves the existing problems by utilizing the effective combination of solid phase polycondensation and direct spinning technology from the two aspects of improving quality and reducing energy consumption. The invention adopts solid phase polycondensation to improve the molecular weight of the recovered polycaprolactam, and then adopts a direct spinning mode to produce the regenerated chinlon 6, as shown in figure 3. The regeneration method provided by the invention is simple and effective, not only can improve the production efficiency and the product quality of the regenerated nylon-6, but also can avoid repeated hot processing of regenerated raw materials and reduce energy consumption.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any changes and alterations made without inventive step within the spirit and scope of the claims are intended to fall within the scope of the invention.
Claims (10)
1. A method for producing regenerated nylon-6 fiber by adopting a solid-phase polycondensation direct spinning technology is characterized by comprising the following steps:
and (3) recovering raw materials: separately collecting waste materials generated in the production process of nylon 6 to obtain blocky waste materials and/or filiform waste materials;
pretreatment of reclaimed materials: chopping the lumpy waste material and/or the filiform waste material;
pre-drying: feeding the pretreated massive waste and/or filamentous waste into a pre-drying tower from the top of the tower, and simultaneously introducing high-temperature nitrogen from the bottom of the pre-drying tower, wherein the nitrogen carries water vapor to flow out from the top of the tower to enter a recovery system;
solid-phase polycondensation: the dried and softened blocky waste and/or filamentous waste flows out from the bottom of a pre-drying tower, and then is fed into a solid phase polycondensation tower for polycondensation reaction, a catalyst is sprayed to the blocky waste and/or filamentous waste from the top of the solid phase polycondensation tower, high-temperature nitrogen is introduced from the top of the solid phase polycondensation tower, the nitrogen flows out from the bottom of the solid phase polycondensation tower and enters a recovery system, and a regenerated nylon raw material in a softened state is obtained at a certain polycondensation temperature and polycondensation time; and
direct spinning: feeding the regenerated nylon raw material into a screw extruder directly for melting, extruding through a spinneret plate, oiling, drafting and winding to obtain the regenerated nylon-6 fiber.
2. The method according to claim 1, wherein the pretreatment of the reclaimed material comprises pulverizing the lump waste to obtain particles having a particle size of 1mm or less.
3. The method according to claim 1, wherein the pretreatment of the recycled material comprises cutting the filamentous waste into short fibers of 2 to 10 mm.
4. The method of claim 3, wherein the staple fibers are washed free of degreaser prior to predrying.
5. The method according to claim 1, wherein the water content of the pre-dried lump waste and/or filamentary waste is controlled to 500 to 5000 ppm.
6. The method according to claim 1, wherein the polycondensation temperature is controlled to 110 to 180 ℃ and the polycondensation time is controlled to 3 to 10 hours.
7. The process of any of claims 1 to 6, wherein the time taken for the recycled nylon feedstock to pass from the feed screw extruder to the extrusion spinneret in direct spinning is less than or equal to 10 minutes.
8. The method according to claim 7, wherein the temperature of the pre-drying tower is controlled to be 100 to 130 ℃, the temperature of nitrogen gas in the pre-drying tower is controlled to be 100 to 140 ℃, and the temperature of nitrogen gas in the polycondensation tower is controlled to be 120 to 180 ℃.
9. The process according to claim 7, wherein the catalyst is used in an amount of 100 to 5000ppm based on the total amount of the spinning melt.
10. The method of claim 7, wherein the catalyst is one or a mixture of any two or more of boric acid, phosphoric acid, potassium dihydrogen phosphate and an aqueous solution of potassium hydrogen sulfate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116180278A (en) * | 2023-02-28 | 2023-05-30 | 江苏阿代尔新材料科技有限公司 | Regenerated fiber production line |
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